Detergent compositions containing gamma-hydroxy organic sulfonate type compounds



United States Patent DETERGENT COMPOSITIONS CONTAINING GAM- MA HYDROXYORGANIC SULFONATE TYPE COMPOUNDS George L. Broussalian, St. Louis, Mo.,assignor to Monsanto Company, St. Louis, Mo., a corporation of DelawareNo Drawing. Filed Dec. 15, 1964, Ser. No. 418,567

11 Claims. (Cl. 252161) ABSTRACT OF THE DISCLOSURE Detergentcompositions containing in addition to conventional detergentingredients from about 5 to 50% by weight of a gamma-hydroxy sulfonatetype compound. The gamma-hydroxy organic sulfonate type compound acts asa supplemental detergent active material and results in the productionof large quantities of foam or lather which is extremely stable in thepresence of greases.

This invention relates to new and useful detergent compositions and toprocesses for preparing them. More particularly, this invention relatesto both aqueous and nonaqueous compositions which contain significantamounts of gamma-hydroxy organic sulfonate type compounds that can berepresented by Formula 1:

o B H l I; S'oat wherein R and R are hydrophobic organic radicalscontaining from 1 to about 21 carbon atoms or hydrogen and the sum ofthe total number of carbon atoms in R plus R is from about 7 to about21; A and B are selected from the group consisting of lower alkyl,halogen, hydrogen, and halogen-substituted lower alkyl radicals; and Mis either hydrogen, an alkali metal cation, an alkaline earth metalcation, or an ammonium cation; and to processes for preparing thesematerials.

The swifty increasing consumption of high foaming household handdishwashing compositions over the past several years both in thiscountry and abroad is conclusive evidence of the increasing value ofthis type of product both to manufacturers of such dishwashingcompositions and to manufacturers of surface active agents (surfactants)that can be utilized in the formulation of such compositions. In view ofthe importance of this end use, a search for new and improved handdishwashing detergents is being conducted practically continuously bymany surfactant manufacturers.

In order to qualify as a useful hand dishwashing surfactant, a materialmust have the ability to cause the formation of large quantities of foamor lather when aqueous solutions of the materials are agitated, whichlather is stable when greases or greasy soils are also dissolved ordispersed therein. It has been discovered that when the above-describedgamma-hydroxy sulfonate-type compounds are utilized in sufiicientamounts or proportions, either with or without other surfactants, inhand dishwashing compositions, for example, unexpectedly largequantities of foam or lather which is extremely stable in the presenceof dissolved greases or greasy soils results therefrom. While extremelysmall amounts of some ICC of the gamma-hydroxy sulfonates describedabove may inadvertently have been produced heretofore (in processes, forexample, in which other types of surfactants were manufactured in verylarge quantities or proportions) the valuable benefits that result fromusing larger amounts were not appreciated heretofore.

It has now been discovered that not only are the abovedescribedga'mmahydroxy organic sulfonate-type compounds of this invention usefulas general purpose surface active agents in aqueous solutions, but theyare particularly useful as agents which produce unexpectedly largequantities of foam or lather when they are dissolved in water, whichfoam or lather is extremely stable in the presence of dissolved and/ordispersed greases. Thus, the compositions of this invention representparticularly useful laundry and dishwashing detergent compositions.

Ordinarily the organic radicals (designated by R and R" in Formula 1,above) that are present in the gammahydroxy organic sulfonate-typecompounds of the present invention can be branched or unbranched topractically any degree without substantially eliminating all of thebenefits that can result from the invention. It is generally preferred,however, that the organic radical(s) be straight-chain in nature. It isstill further preferred that the sum of the total number of carbon atomsin R and R be between about 9 and about 17. Although organic radicals Rand R can contain heterocyclic, monocyclic hydrocarbyl and polycyclichydrocarbyl 'radials (whether the rings are saturated or not), and canalso contain substituents such as halides (including for example,fluoride, chloride, bromide and iodide), ester groups, ether groups,thioether groups, amine groups, nitrile groups, amide groups, and thelike, in their otherwise aliphatic or alicyclic radicals, it ispreferred that R and/ or R be either hydrocarbyl in nature or that theycontain only halide substituents in their otherwise hydrocarbylradicals. Also, it is particularly preferred that the sulfonate group(in the above-described gamma-hydroxy organic sulfonate type compoundsthat are contemplated for use in the practice of this invention) beattached to the carbon atom which is at an end of a long chainhydrophobic organic radical (preferably alkyl), and that the singlehydroxy group appear attached to the third carbon atom in the same longchain. For example, these particularly preferred compounds justdescribed include those having a structure such as that illustrated inFormula 2:

( H H H -CC--CH l (i) S 0 3M H wherein R is a higher alkyl radical,preferably containing from about 9 to about 17 carbon atoms, and M is analkali metal cation. Of these compounds, those having straight chainalkyl groups are even further preferred.

While from the above discussion it can be seen that the alkali metalsulfonate salts are preferred forms of the above-described gamma-hydroxysulfonate-type compounds, it is nevertheless :a fact that ammoniumsalts, as well as alkaline earth metal salts (where, for example, M in'Formulas 1 and 2, above, represents /zCa /2Mg++, /2Ba++, /zSr++ or/2Ra++) can be used in the practice of this invention. Of the preferredalkali 3 metal salts (including Li, Na, K, Rb, Cs, Fr) the sodium andpotassium salts are particularly preferred, especially from thestandpoint of cost.

Typical, but non-limiting examples of the gammahydroxy organicsulfonate-type compounds that are useful in the practice of the presentinvention include ammonium 2-methyl-3-hydroxy-l-octadecanesulfonate,

sodium 3-hydroxy-l-pentadecanesulfonate,

potassium 4-(branched) dodecyl-4-hydroxy-2-butanesulfonate,

ammonium 5-hydroxy-3-octadecanesulfonate,

sodium 3-(branched) pentadecyl-3-hydroxy-l-propanesulfonate,

ammonium 1-isopropyl-3-(9, lO-dichloroheptadecyl) -3-hydroxy-1-propanesulfonate,

potassium 3-hydroxy-l-dodecanesulfonate,

sodium l-phenyl-3-hydroxy-l-hexadecenesulfonate,

sodium '2-brom-o-3-hydroxy-l-hexadecanesulfonate,

potassium 1- 3-pyridyl l-hydroxy-3-hexadecanesulfonate sodium3-hydroxy-l-hexadecanesulfonate,

magnesium 3,3-dioctyl-3-hydroxy-l-propanesulfonate,

sodium 3-methyl-3-hydroxy-l-octadecanesulfonate,

sodium 3-(branched) dodecyl-S-hydroxy-l-propanesulfonate,

calcium l-hydroxy-3-tetradecanesulfonate,

sodium l-trichlorometbyl-1-hydroxy-3-hexadecanesulfonate,

sodium l-carbamido-l-hydroxy-3-pentadecanesulfonate potassium4-autoxy-5-hydroxy-3-nonadecanesulfonate,

sodium 1-hydroxy-3-octadecanesulfonate,

sodium 3-(branched dodecylphenyl)-3-hydroxy-l-propane sulfonate,

magnesium 2-hydroxy-4-pentadecanesulfonate,

sodium l-hydroxy-2-cyano-3-pentadecanesulfonate,

strontium 3-hydroxy-l-tetradecanesulfonate,

sodium l-amino-2-hydroxy-4-hexadecanesulfonate, and

ammonium 1-methoxy-4-hydroxy2-heptadecanesulfonate.

The gamma-hydroxy organic sulfonates of the present invention can bemanufactured by one of several methods. One method is to react anappropriate Grignard with beta-chloropropionaldehyde followed bysulfitation with sulfite ion. Another method is to react an appropriateacid chloride and olefin in the presence of a Friedel-Crafts catalyst toyield an alpha,beta-unsaturated ketone followed by free radical additionof bisulfite ion and their reduction with hydrogen, either catalyticallyor chemically. Still another method is to hydrolyze the correspondinggamma-sultone with water or base, preferably in basic methanol.

The gamma-hydroxy sulfonate-type compounds that are useful in thepractice of the present invention can be utilized advantageously asgeneral purpose detergent active ingredientseither alone or incombination with practically any material that can be employed incombination with known organic detergent anionic and nonionic surfaceactive agents, such as soap, the alkali metal fatty alcohol sulfates,the alkali metal, ammonium, and alkaline earth metal alkylarylsulfonates; higher alcoholethylene oxide condensates, alkylphenolethylene oxide condensation products, fatty acid-ethylene oxidecondensation products, for example, sodium dodecylbenzene sulfonates,vicinal acylamido alkane sulfonates, vicinal amino alkane sulfonates,olefin sulfonates; and other similar surfactants. The types of materialsthat can 'be employed in the formulation of so-called polyphosphatebuilt detergents, flake and powdered compositions (presuming the usualconditions of compatibility are applied) include such materials as otherorganic anionic 'and/or nonionic and/or ampholytic surface active agentsor materials, polyphosphate complexing agents and other inorganic andorganic builders, anti-redeposition agents, optical brighteners,bleaching agents, and the like; all of which are well-known in thedetergent art and need not be detailed here. It is interesting to notethat the gammahydroxysulfonatetype materials of this invention can beutilized advantageously in practically any of the compositions in whichthe alkylaryl sulfonates, for example, can be utilized. It should benoted, however, that whenever these gamma-hydroxy sulfonates areutilized in combination with other organic surface-active agents such asthe higher alkyl benzene sulfonates, for example, generally in order forthe unexpectedly desirable properties of the gamma-hydroxy sulfonate tobecome readily apparent when the mixture or combination of organicsurfactants is ultimately dissolved in Water, the amount of thegamma-hydroxy sulfonate in the organic surfactant combination should beat least about 10 weight percent, based on the total combined weight ofthe organic surfactants in the combination. Preferably, this proportionof the gamma-hydroxy sulfonate should be at least about 15 weightpercent of the total amount of organic detergent surface activeingredients in any aqueous or nonaqueous composition in which they areutilized.

The gamma-hydroxy sulfonates described above are particularly usefulwhen they are formulated into socalled built detergent compositions andused as such, for example, as light duty or heavy duty launderingdetergents. Built detergents are those that contain, in addition to thedetergent active material, at least one water-soluble inorganic buildersalt such as an alkali metal pyrophosphate, tripolyphosphate, carbonate,sulfate, or the like. In such built detergent compositions, theoutstanding properties of the sulfonates of the present invention canreadily be appreciated when the composition contains at least about 5Weight percent, and up to about weight percent or more; preferably fromabout 10 to about 35 weight percent, of these gamma-hydroxysulfonate(s).

As it was stated hereinbefore, the gamma-hydroxy sulfonates describedabove can advantageously be utilized along with any other anionic,nonionic, or ampholytic detergent active materials (surfactants) ormixtures thereof in the proportions specified above. The term anionicsurfactants, encompasses such materials as the alkali metal salts offatty acids and fatty acid derivatives, commonly known as soaps (such assodium la-urate, sodium palmitate, and the potassium salts of coconutfatty acids); the alkali metal salts of sulfuric esters [such as sodiumlauryl alcohol sulfate, potassium hexadecanol sulfate, lithium petroleumalcohol (average C chain length) sulfate as well as the alkali metalsulfates of condensation products of alcohols containing from about 10to about 30 carbon atoms with from about 2 to about 40 moles of a loweralkylene oxide such as ethylene oxide, propylene oxide, or mixturesthereof]; the alkali metal salts of alkanesulfonates, preferablystraight-chain alkanesulfonates (such as those prepared by sulfonatingcertain petroleum fractions with S03); the alkali metal and alkalineearth metal salts of esterand ether-linked sulfonates [such as thesodium dialkyl sulfosuecinates (wherein alkyl contains from about 4 toabout 20 carbon atoms), the potassium lauryl diester of2,3-dihydroxypropane-lsulfonate]; amide-linked sulfonates (such assodium oleylmethyltaurate, sodium 4-acyl-aminobutane-l-sulfonates, andsodium myristyl sulfomethylamide); alkylarylsulfonates wherein thesingle alkyl group preferably contains from about 10 to about 20 carbonatoms (such as sodium dodecylbenzene sulfonate); mahogany and petroleumsulfonates; vicinal acylamido alkane sulfonates; vicinal amino alkanesulfonates; olefin sulfonates; and the like. The term nonionicsurfactants encompasses such materials as the condensation products ofseveral moles of a lower alkylene oxide such as ethylene-, propylene-,or butylene-oxide with a mole of a higher alkyl alcohol, alkylphenol,fatty acid, and the like (wherein the alkyl group contains from about 10to about 20 or more carbon atoms); the fatty alkanolamides (such as thediethanolamide of tall oil fatty acids and the diethanolamide of lauricacid); and the polyhydroxy nonionic surfactants (such as sorbitolmonolaurate, and the reaction products of fatty primary amines withdeltagluconolactone). The ampholytic surfactants contain both acidic andbasic functional groups in their individual molecules, and include suchmaterials as dodecyl-beta-alanine, sodium N- dodecyl taurate, and theproducts from reacting benzene amino sulfonic acid, for example, withn-hexadecylchloride. Other examples of organic anionic, nonionic andampholytic surfactants that can also be present in compositionscontaining the gamma hydroxy sulfonate materials described above can befound in Surface Active Agents and Detergents, by Schwartz et :al.,Interscience Publishers, Inc., New York (1958), volume II.

The pure gamma-hydroxy sulfonate compounds of this invention as well ascompositions containing them such as those described above, havephysical and chemical properties that make them particularly outstandingdetergents for use in the form of aqueous solutions (containing them) toclean various solid substrates in the presence of dissolved anddispersed greases, for example, as a hand dishwashing detergentcomposition. In a standard test designed to closely examine thesuitability of various water-soluble surface active agents for use inthe for-mulation of high foaming hand dishwashing detergents, sodiumB-hydroxy-l-n-pentadecane sulfonate cleaned 18 plates before the foam orlather on the surface of the test solution broke, while sodiumdodecylbenzene sulfonate (made from a tetrapropylene olefin) effectivelywashed only about 7 plates before the lather broke when it was used inthe same test under practically identical conditions. These high-foamingbeneficial properties of the gamma-hydroxy sulfonates of this inventioncan be readily appreciated when these materials are present (dissolved)in water at a level of at least about 0.005 weight percent (so that theyrepresent at least about 10 weight percent of the total surfactanttherein). For optimum results, this level should be generally betweenabout 0.010 and about 20 weight percent, and preferably between about0.015 and about 10 weight percent of the total aqueous solution weight.

In the following example, which is illustrative of one of the preferredembodiments of this invention, all parts are by weight unless otherwisespecified.

EXAMPLE I Process To cold C.) Grignard material prepared by reacting 125parts of n-l-bromododecane with 14 parts of magnesium (powder) inanhydrous ethyl ether is added slowly, with stirring, a cold C.)solution of 53 parts of beta-chloropropionaldehyde (prepared accordingto the procedure of Jacobs and Weinstein, J. Org. Chem., vol. 11, p.225, 1946) in 200 parts of ethyl ether. The resulting mixture is warmedslowly (over 1 hour) to room temperature. After stirring for about 3hours at room temperature the mixture is permitted to stand for 15minutes. Two layers separate. The top (ether) layer contains 140 partsof crude S-hydroxy-l-chloropentadecane. Treatment of this material(after evaporation of the ether) with 700 parts of potassium sulfite,1000 parts of water and 750 parts of methanol by heating the mixture atreflux for 16 hours, followed 'by cooling to 0 C., and filtering, yields155 parts of practically pure potassium3-hydroxy-l-pentadecanesulfonate.

The residue (after removal of the solvent mixture) from Example I isitself an excellent very high foaming surfactant; yielding an extremelyhigh volume of foam when it is dissolved in water at a level of about0.1 weight percent and the water is subsequently agitated, which foam isunexpectedly stable in the presence of dissolved greases, as forexample, after many greasy dishes are washed in the aqueous solution.

A procedure such as that described in either Example I, above, or in theliterature referred to hereinbefore, can be utilized to manufacture anyof the gammahydroxy sulfonates useful in the practice of the presentinvention.

For the sake of convenience and more ready understanding of theaforementioned fundamentals of the present invention, the gamma-hydroxyorganic sulfonate-type compounds of this invention have generally beenreferred to as though they were pure components, containing for examplehydrophobic radicals, alkyl groups, and the like [as R and R in Formulae1 and 2] which are all identical. It is well known by those skilled inthe art, however, that a high degree of purity in such compounds is veryrarely if ever attainable in practical commercial operations formanufacturing detergents. Thus, in practice when a particular chainlength such as dodecyl, hexadecane, octadecene, and the like arereferred to, almost invariably these terms mean that these are theaverage chain lengths in the particular surfactant materials beingdescribed, and that, in addition to dodecyl, for example, some chainlengths varying to some extent from C in length can be (and generallyare) present therein. Similarly, where terms are utilized hereinreferring to a particular chain length such as hexadecane, tetradecane,and the like, it is intended that this be about the average chainlength, and that the term encompasses mixtures of materials having chainlengths varying to some extent from the named average chain length. Itis generally preferred, however, that such mixtures of materials containat most about 10 weight percent of materials varying more than about 3carbon atoms on either side of the named average. For example, the termsodium 3-hydroxy-l-hexadecanesulfonate includes not only the purehexadecane material but also mixtures containing from about tridecane toabout nonadecane wherein the average chain length of the mixture is Cand less than a total of 10 weight percent of the materials in themixtures have chain lengths less than C or more than C Generally, insuch mixtures, material containing the named average number of carbonatoms will be the largest single component in the mixtures.

Table 1, below, illustrates the valuable benefits which can be obtainedwhen the preferred gamma-hydroxy sulfonates of this invention areutilized as laundering detergents.

TABLE 1.DETERGENCY LDATA Compound: Detergency Sodium 2-bromo-3-hydroxy-1 hexadecanesulfonate 115 Sodium 3-hydroxy-1 hexadecansesulfonate 117Sodium 3-hydroxy-l-mntadecanesulfonate 118 Potassium 4-(branched)dodecyl 4-hydroxy-2- butanesufonate 110 Potassium3-hydroxy-l-dodecanesulfonate Sodium 1-hydroxy-3-octadecanesulfonatePotassium 4-autoxy-5-hydroxy 3 nonadecanesulfonate Strontium3-hydroxy-l-tetradecanesulfonate 110 60 Sodium 3-(branched)pentadecyl-3-hydroxy 1- propanesulfonate Sodium 1-phenyl-3-hydroxy 1hexadecenesulfonate 112 Ammonium 2-methyl-3-hydroxy-1 octadecane- 65sulfonate 113 Magnesium 3,3-dioctyl-3-hydroxy-l-propanesulfonate 98Standard Na DDBSA (from tetrapropylene) 103 1 p .p.m. hard water. Testdescribed by Jay C. Harris in 70 lgElrlluatron of Surface Active AgentsASTM Bulletin, May

Table 2, below, illustrates the very valuable benefits that can beobtained by utilizing these materials as hand dishwashing detergentsboth alone and in combination with other surface active agents. Detailson the test procedure for evaluating hand dishwashing detergents aredescribed after Table 2.

TABLE 2.EVALUA'J]ION AS HAND DISHVVASHI NG 1 Sodium dodecylbenzenesulfonate made from tetrapropylene; average C12 alkyl group.

This hand dishwashing test involves the washing; by hand of nineinchdinner plates which are pre-soiled with one teaspoonful each of asynthetic soil mixture consisting of 75 weight percent of shortening and25 weight percent of flour. Washing of the plates is performed (using adishcloth to remove the synthetic soil) in 4 liters of water having aninitial temperature of about 50 C. and containing 0.075 weight percentof the surfactant or surfactant mixture being tested. The number ofplates washed cleaned in the formal fashion by the time the lather ofthe dishpan has broken to the extent that less than half of the surfaceremains covered with lather. The manipulative procedures of this testare described in greater detail in the Proceedings of the,43rd AnnualMeeting of the Chemical Specialties Manufacturers Association, December1956; Procedure No. 3, page 191.

In the following Table 3 are tabulated data showing some typicalsurfactant properties of one of the outstanding preferred gamma-hydroxysulfonates of the present invention (practically pure sodiumB-hydrOXy-I-npentadecane sulfonate).

TABLE 3.SURFACTANT EVALUATION DATA Test Concentration Results (wt.percent) D etergency 1 Ross-Miles Lather Z 1 In 150 p.p.1n. hard water.Test described by Jay C. Harris in Evalu ation of Surface Active AgentsASTM Bulletin, May, 1946.

1 50 0. Values taken 5 minutes after lather was formed.

3 Room temperature, in distilled water.

What is claimed is:

1. A detergent composition consisting essentially of at least onematerial selected from the group consisting essentially of anionicdetergent active materials, nonionic detergent active materials andampholytic detergent active materials, and additionally containing, as asupplemental detergent material, from about 5 to about 50 weight percentof a gamma-hydroxy sul fonate-type compound having the formula wherein Rand R are selected from the group consisting of saturated andmonoethylenically' unsaturated hydrophobic hydrocarbon radicalscontaining from 1 to 21 carbon atoms, halogen substituted saturatedhydrocarbon radicals containing from 1 to 21 carbon atoms and hydrogen,the sum of the total number of carbon atoms in is determined by thenumber of plates which can be' 8 R plus R is from about 7 to about 21; Aand B are selected from the group consisting of lower alkyl, halogen,hydrogen, and halogen-substituted lower alkyl radicals; and M is acation selected from the group consisting of alkali metal, ammonium,alkaline earth metal and hydrogen'cations.

2. A composition as in claim 1, wherein said composition containsbetween about 10 and about 50 weight percent of said sulfonate-typecompound, R is an alkyl radical containing from about 9 toabout 17carbon atoms, R is hydrogen, A and B are hydrogen, and M is an alkalimetal cation.

3. A detergent composition as in claim 1 wherein R and R in eachinstance represent a member selected from the group consisting ofhydrogen and alkyl radicals and wherein A and B in each instancerepresent a member selected from the group consisting of hydrogen andlower alkyl radicals.

4. A composition as in claim 2 containing an inorganic detergencybuilder salt.

5. A detergent composition consisting essentially of a first detergentactive material selected from the group consisting of organic anionicand nonionic surface active agents and at least about 10 weight percent,based on the total weight of organic detergent active materials in saidcomposition, of a second detergent active material; said seconddetergent active material being a sodium 3- hydroxy-l-sulfonate havingthe formula wherein R is an alkyl group containing from about 7 to about21 carbon atoms.

6. A composition as in claim 5, wherein said sodium3-hydroxy-l-sulfonate is a mixture of sulfonates having single alkylgroups containing from about 12 to about 20 carbon atoms, wherein theaverage chain length of said alkyl groups is from about 12 to about 17carbon atoms, and wherein said detergent composition contains aninorganic detergency builder salt.

7. A built detergent composition consisting essentially of at least oneinorganic detergency builder salt, and, as an organic detergent activefrom about 5 to about 50 weight percent of a gamma-hydroxy sulfonatehaving the formula wherein R and R are selected from the groupconsisting of saturated and monoethylenically unsaturated hydrophobichydrocarbon radicals containing from 1 to 21 carbon atoms and hydrogen,the sum of the total number of carbon atoms in R plus R is from 7 to 21,and M is an alkali metal cation.

8. A built detergent composition as in claim 7, wherein said hydrophobichydrocarbon radicals are alkyl radicals.

9. A built detergent composition as in claim 8, where in said alkalimetal cation is sodium and said sulfonate is a mixture of sulfonateshaving from about 10 to about 24 carbon atoms in their alkyl groups andthe average chain length of said alkyl groups is from about 12 to about20 carbon atoms.

10. A built detergent composition as in claim 8, wherein R is hydrogenand the average number of carbon atoms in R is about 12.

11. A detergent composition consisting essentially of an inorganicdetergency builder salt and from about 5 to about 50 weight percent of agamma hydroxy sulfonate type compound having the formula:

wherein R and R are selected from the group consisting of saturated andmonoethylenically unsaturated hydrophobic hydrocarbon radicalscontaining from 1 to 21 carbon atoms, halogen substituted saturatedhydrocarbon radicals containing from 1 to 21 carbon atoms, and hydrogen,the sum of the total number of carbon atoms in R plus R is from about 7to about 21; A and B are selected from the group consisting of loweralkyl, halogen, hydrogen, and halogen-substituted lower alkyl radicals;and M is a cation selected from the group consisting of alkali metal,ammonium, alkaline earth metal and hydrogen cations.

References Cited UNITED STATES PATENTS 2,793,229 5/ 1957 laser.

3,115,501 12/1963 Finch et al. 260-613 3,164,608 1/1965 Blaser.

3,164,609 1/1965 VOss et al.

LEON D. ROSDOL, Primary Examiner.

P. E. WILLIS, S. D. SCHNEIDER, S. DARDEN,

Assistant Examiners.

